DE19958471A1 - Controlled release detergent, e.g. laundry or dishwasher detergent, contains active ingredient, optionally on carrier, finished, e.g. coated, with polymer with lower critical separation temperature - Google Patents

Abstract

Laundry and other detergents (A) containing usual ingredients contain an active formulation finished with an LCST polymer (I) (material with a lower critical separation temperature). An Independent claim is also included for laundry and other detergents (B) containing usual active and other ingredients, with active ingredients (partly) finished with (I), in which part of the active ingredients is applied to carrier materials.

Description

The present invention relates to a washing and cleaning agent containing conventional Ingredients and a preparation containing an active ingredient, the active ingredient and contains an LCST substance.

The controlled release of active substances plays a role wherever the active substance not immediately after delivery but only at a certain point in time Procedure should have its effect. In many cases, the active ingredients that are only in one metered later stage, are fed manually.

In the pharmaceutical sector, this is used for active ingredients to be administered orally different solution behavior of polymers in acidic and alkaline environments, d. H. how in the stomach and intestines by using such polymers for coating tablets etc. be used. Medications that are supposed to get into the intestine are common coated with a gastric juice-resistant polymer that only dissolves in the intestine.

In other processes, temperature curves are run through, for example in the Sterilization and pasteurization of food.

Washing and cleaning processes also have several heating and cooling phases. In particular, in the last process stage, e.g. B. the last rinse one Washing machine or in the last rinse of a dishwasher, in the so-called Rinse aid, various active ingredients added. These active ingredients are used in the usual Washing and cleaning procedures are usually added as separate agents, but are not contained in the actual washing or cleaning agent.

In the international patent application WO 98/49910 an encapsulated material discloses, wherein at least a portion of the material during a heat treatment in a encapsulated in an aqueous environment and after cooling after this heat treatment is released. This material is coated with a layer of a hydrophobic film Material and a layer that is a material with a lower critical separation temperature  (LCST polymer), which is below the temperature of the heat treatment. The Encapsulated materials are used in the food industry in sterilization processes used.

The present invention was based on the object of a washing and cleaning agent To provide that contains an active ingredient that is in a washing or Cleaning process that goes through one or more temperature levels only after one Heat treatment, e.g. B. is only released in a rinse aid.

Surprisingly, it was found that active ingredients in washing and The cleaning process can only be released in a rinse aid if: these active ingredients to be incorporated into the agents are made up with an LCST substance.

The present invention relates to a detergent and cleaning agent usual ingredients, characterized in that it contains an active ingredient preparation which is made up with an LCST substance.

LCST substances are substances that are active at low temperatures have better solubility than at higher temperatures. They are also called Substances with a lower critical separation temperature.

Active substance preparation in the sense of the present invention means that this preparation contains an active ingredient and possibly other ingredients and with an LCST substance is made up. In one possible embodiment, the preparation with the LCST Substance coated or enveloped. In a further embodiment, the LCST Substance as matrix material for the active ingredient.

The preparation of the active substance preparation can be carried out in a manner known per se and depends on the formulation of the finished agent. The preparation can e.g. B. by simply mix the individual ingredients. It is also possible that Granulate or extrude ingredients of the preparation. Will the LCST substance applied as a coating, the individual ingredients of the preparation as Granules or extrudates are pre-assembled and then coated. The Active substances can also be produced in the form of capsules, the LCST polymer itself can represent the capsule wall or subsequently to one containing the active ingredient Capsule is applied. It doesn't have to be a single capsule.  

Likewise, a composite of capsules, the z. B. by gluing or pressing individual Capsules are created, can be used.

In a further embodiment, the LCST substance forms a matrix material. In this Embodiment can e.g. B. an active ingredient-containing mixture can be produced with a LCST substance is coated. The mixtures obtained can either be in the form of Granules are present and then, if necessary in the presence of other ingredients, in itself known way, such as by pressing, processed into a shaped body. On the other hand, it is also possible to use the mixture as a sol or as a melt to process further.

The washing and cleaning agent can be used particularly advantageously in mechanical processes use where the active ingredient is released in one rinse after the washing step should. Examples are machine textile washing and machine cleaning of dishes both in the household and in the commercial sector. By the invention The active ingredients remain in a liquid after heat treatment Medium, e.g. B. after the main rinse or wash, at least partially unchanged and the active ingredient is only after cooling after the heat treatment, i.e. in Rinse cycle, released.

According to the present invention, the delayed-release active ingredient is combined with a Assembled LCST substance. LCST substances are substances that lower temperatures have a better solubility than at higher temperatures. They are also referred to as substances with a lower critical segregation temperature. These substances are usually polymers. Depending on the application conditions, the lower critical separation temperature between room temperature and the temperature of the Heat treatment, for example between 20 ° C, preferably 30 ° C and 100 ° C, especially between 30 ° C and 50 ° C. The LCST substances are preferred selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, Polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these Substances.

Examples of alkylated and / or hydroxyalkylated polysaccharides are methylhydroxypropyl methyl cellulose (MHPC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), carboxy methyl methyl cellulose (CMMC), hydroxybutyl cellulose (HBC), hydroxybutyl methyl cellulose (HBMC), hydroxyethyl cellulose (HEC), hydroxyethyl carboxymethyl cellulose (HECMC), hydroxyethyl ethyl cellulose  (HEEC), hydroxypropyl cellulose (HPC), hydroxypropyl carboxy methylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulo se (MHEC), methylhydroxyethyl propyl cellulose (MHEPC), methyl cellulose (MC) and propyl cellulose (PC) and mixtures thereof, carboxymethyl cellulose, methyl cellulose, Methylhydroxyethylcellulose and methylhydroxyproplcellulose as well as the alkali salts of the CMC and the slightly ethoxylated MC or mixtures of the foregoing are preferred.

Further examples of LCST substances are cellulose ethers and mixtures of Cellulose ethers with carboxymethyl cellulose (CMC). Other polymers that have a lower show critical separation temperature in water and which are also suitable Polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N- substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the above (co) polymers. Are suitable also polyethylene oxide or copolymers thereof, such as ethylene oxide / propylene oxide copo polymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymeth acrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain pro teine like Poly (VATGVV), a repeating unit in the natural protein elastin and certain alginates. Mixtures of these polymers with salts or surfactants can can also be used as an LCST substance. By such additions or by Degree of crosslinking of the polymers can be the LCST (lower critical separation temperature) be modified accordingly.

In a preferred embodiment of the present invention, the Active ingredients used according to the invention coated with a further material which at a temperature above the lower segregation temperature of the LCST substance is soluble or a melting point above this temperature or a retarded Has solubility, that is above the lower separation temperature of the LCST layer can be released. This layer is used to mix the active ingredient and LCST Substance in front of water or other media that dissolve it before the heat treatment can protect. This additional layer should not be liquid at room temperature and preferably has a melting point or softening point at a temperature which equal to or above the lower critical segregation temperature of the LCST polymer lies. The melting point of this layer is particularly preferably between the lower one critical segregation temperature and the temperature of the heat treatment. In a Special embodiment of this embodiment are the LCST polymers and the further substance mixed together and applied to the material to be encapsulated.  

The further substance preferably has a melting range that is between approximately 35 ° C. and is about 75 ° C. In the present case, this means that the melting range within the specified temperature interval occurs and does not indicate the width of the melting range. The properties mentioned above are usually fulfilled by so-called waxes.

"Waxing" is understood to mean a number of natural or artificially obtained substances that usually melt above 35 ° C without decomposition and a little above the Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility. They are divided according to their origin Wax in three groups, the natural waxes, chemically modified waxes and the synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as Beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin wax or micro wax.

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Can also be used as coating materials Compounds from other classes of substances which meet the requirements mentioned with regard to the Meet softening point. Suitable synthetic compounds have been found for example higher esters of phthalic acid, especially dicyclohexyl phthalate, the is commercially available under the name Unimoll® 66 (Bayer AG). Are suitable also synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea) is. Conversely, synthetic or semi-synthetic esters from lower alcohols are also included Fatty acids from native sources can be used. Tegin®, for example, falls into this class of substances 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS-Dreiring-SP (Kalkhoff GmbH) can be used as another substance.  

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols usually with about 22 to 40 carbon atoms. The Wax alcohols come in the form of wax esters of higher molecular fatty acids, for example (Wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The Coating may also contain wool wax alcohols, including Triter Penoidal and steroidal alcohols, for example lanolin, understands that, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least proportionately as Part of the coating can be used in the context of the present invention Fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-insoluble ones or only slightly water-soluble polyalkylene glycol compounds.

Other suitable substances with a melting point above the LCST of the one below Coating material are saturated aliphatic hydrocarbons (paraffins).

All water-soluble in water are also suitable as coating materials dispersible and water-insoluble polymers that have a melting point that above the lower critical separation temperature of the used according to the invention LCST polymer is or are soluble above this temperature. Suitable polymers are at room temperature solid polyethylene glycols, polyvinyl alcohols, polyacrylic acid and their Derivatives. Furthermore, gelatin has also proven to be suitable.

Sometimes it can be sufficient to protect the LCST polymer layer when it is through a water-soluble coating is shielded from initially cold water. This Water-soluble coating only has to have a sufficiently delayed solubility, so that the layer is stable for a sufficiently long time. For this, e.g. B. polyalkylene glycols preferably higher molecular weight can be used.

The active ingredient used and delayed release can be used in a manner known per se processed the LCST substance and / or the further material, d. H. be assembled. The substances are used as a coating on the active ingredient or the preparation applied, the substances z. B. as a melt or in the form of a solution or Dispersion can be sprayed on, or the mixture can be in the melt, solution or Dispersion can be immersed or mixed with it in a suitable mixer. That too Coating in a fluid bed apparatus is possible. All are suitable for the spraying process Processes established in pharmacy and food technology for the production of  coated tablets, capsules and particles. The polymer suspension or solution is sprayed either discontinuously in small portions, the particles z. B. on transported on a conveyor belt through a liquid curtain and then in the Airflow can be dried or continuously while drying by the injected air flow in fluidized bed, fluidized bed or flight bed wrapping devices sprayed. The coating process is also conceivable if the coating syrups are LCST polymers are added in a sufficiently high concentration. The application of the second layer is done analogously.

A major advantage of the washing and cleaning agent according to the invention is that Active substances that are released in a process step after a heating step should, d. H. in rinse aid, do not need to be added separately. Most laundry and cleaning processes both in the commercial sector and in the household different temperature levels. Especially in the case of machine processes, the So-called rinse cycles, which are a washing or cleaning stage at elevated temperature follow, usually added further components. These are later stages of the process usually rinse aid rinses, in which the users, depending on the process, certain active ingredients clog. These active ingredients are usually dosed either manually or separately or using specially designed devices. With these processes, too Use of the active ingredients assembled according to the invention has a number of advantages.

Enzymes, fragrances, dyes come as active ingredients in detergents and cleaning agents Acids and bleaching agents based on halogen or oxygen together with bleach activators or - catalysts. Machine dishwashing detergents additionally contain in particular Rinse aid surfactants and corrosion inhibitors. Textile detergents usually contain in addition the components mentioned as active ingredients fluorescent agents, optical brighteners, Enema preventers, textile anti-crease agents, antimicrobial agents, germicides, Fungicides, antioxidants, antistatic agents, ironing aids, phobing and impregnating agents and UV absorbers and fragrances. According to the invention, these active ingredients are treated with an LCST Substance packaged and can be incorporated into the agent according to the invention. In the washing process, they are washed in one rinse after the main rinse or wash released.

In addition to the active ingredients, the detergents and cleaning agents contain other ingredients for example surfactants, preferably selected from the anionic, nonionic, cationic and amphoteric surfactants. The surfactants are preferably present in an amount from 0.1 to 50% by weight, based on the composition.  

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and preferred by average 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO to 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol holoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, especially fatty acid methyl esters.  

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dime thylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula III,

in the RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups . The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula IV,

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can be reacted, for example, with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.  

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulf oxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

As alk (en) yl sulfates, the alkali and especially the sodium salts of sulfuric acid are half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example made from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates are also suitable anionic surfactants.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid gly Cerinestern are to be understood as the mono-, di- and triesters and their mixtures, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _{12 18} fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in surfactant compositions or cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8 18} fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other suitable anionic surfactants include soaps, in particular can be used at higher pH values. Saturated and unsaturated are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or tri ethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

Another group of ingredients are the builders. In the invention Detergents and cleaning agents can all usually be found in detergents and Builders used in cleaning agents, in particular zeolites, Silicates, carbonates, organic cobuilders and / or phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _2x + 1. H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ . yH ₂ O preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

n Na ₂ O. (1 - n) K ₂ O. Al ₂ O ₃ . (2-2.5) SiO ₂ . (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) on and included preferably 18 to 22% by weight, in particular 20 to 22% by weight of bound water.

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. Have among the variety of commercially available phosphates  the alkali metal phosphates with particular preference for pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and Detergent industry the most important.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm-3, melting point 60 °) and as a monohydrate (density 2.04 gcm-3). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO4, is a white salt with a density of 2.33 gcm-3, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water .

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1 , 52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4. Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the crystal water-free salt dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and Potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the machine according to the invention Dishwashing detergents, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are as follows described.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function. For example these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or detergents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.  

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{W of} the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The amount of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which act as monomeric salts of the Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as  Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

Further preferred copolymers are those which are preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and can be used Dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. An oxidized oligosaccharide is also suitable, a product oxidized at C _{6 of} the saccharide ring being particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts.  

Glycerol disuccinates and are also preferred in this context Glycerol trisuccinate. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt the DTPMP. Preferred as a builder from the class of phosphonates HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the means also contain bleach, may be preferred, aminoalkane phosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth ions train as cobuilders.

Another class of active substances contained in the agents according to the invention are bleaches that can be selected from the group of Oxygen or halogen bleaches, especially chlorine bleaches.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the shaped bodies. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoper phthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxythanoic acid [phthalimidhexoxy acid] (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, 2-diperoxyacyloxyacid, diperoxysebacic acid, 2-diacidoxyacid, -Decyldiperoxybutan-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing compounds can also be present as bleaching agents. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable. The The above-mentioned compounds are preferably used in dishwashing detergents used, their use in textile detergents should not be excluded.

In order to achieve an improved bleaching effect, bleach activators can be used in the agents according to the invention are incorporated. Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used. Suitable substances are those that and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-  dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially 1,3,4,6- Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetyl citrate (TEOC), Carboxylic anhydrides, especially phthalic anhydride, isatoic anhydride and / or Succinic anhydride, carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, isopropenylacetate, 2,5- Diacetoxy-2,5-dihydrofuran and the enol esters as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or Triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam and N-acetylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also used preferably used. Combinations of conventional bleach activators can also be used be used. Nitrile derivatives such as cyanopyridines, nitrile quats and / or Cyanamide derivatives are used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, undecenoyloxybenzenesulfonate (UDOBS), Sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12). Such bleach activators are in usual amount range from 0.01 to 20 wt .-%, preferably in amounts of 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the total Composition.

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are suitable as bleaching catalysts Compounds are preferably used, which are described in DE 197 09 284 A1.

Enzymes are used in the washing and cleaning agents according to the invention in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of mentioned enzymes in question. All of these hydrolases contribute to the removal of Soiling such as stains containing protein, fat or starch. To bleach  can also be used oxidoreductases. Are particularly well suited Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetic engineering modified variants obtained enzymatic active ingredients. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus won, used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from Protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. To the suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight. The enzymes can be used in both washing and cleaning processes during the heat treatment as well as in the rinse cycle after the heat treatment, in a mixture with the LCST substance.

Dyes and fragrances can be added to the agents according to the invention in order to to improve the aesthetic impression of the resulting products and the consumer in addition to performance, a visually and sensorially "typical and distinctive" product to provide. Individual as perfume oils or fragrances Fragrance compounds, e.g. B. the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol, the hydrocarbons mainly include terpenes such as limonene and  Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also contain natural fragrance mixtures as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention be, but it can also be advantageous to apply the fragrances to carriers that the Increase the perfume's adhesion to the laundry and by a slower fragrance release ensure a long-lasting fragrance of the textiles. As such carrier materials have become For example, cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries. It is also possible to use the fragrances to be packaged with an LCST substance so that it is only released in the rinse cycle become, which leads to a scent impression when opening the machine.

In a preferred embodiment of the present invention, the one with the LCST Substance made up active ingredient selected from the group of surfactants. The presence of surfactants in the final rinse cycle of a machine dishwashing process has a positive effect the shine and the reduction of limescale deposits. As active ingredients in the rinse aid only weakly foaming nonionic surfactants are usually used. The Use of other surfactants e.g. B. anionic surfactants is not excluded.

As further active ingredients that can be incorporated into agents according to the invention or can also be released in the main rinse or wash cycle, as machine Detergents used contain corrosion inhibitors. The Corrosion inhibitors are used in particular to protect the dishes or the machine contain, especially silver protection in the field of automatic dishwashing have a special meaning. The known substances from the stand can be used of the technique. In general, silver protection agents can be selected from the group of Triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferred to benzotriazole and / or alkylaminotriazole are used. One finds in In addition, detergent formulations often contain active chlorine agents that corrode significantly reduce the silver surface. Chlorine-free cleaners are special Organic and redox-active compounds containing oxygen and nitrogen, such as two and  trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, the are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and Manganese sulfate. Zinc compounds can also be used to prevent corrosion on Washware can be used.

Detergents and cleaning agents that are used for textile washing can be used as Active ingredients that are only released in the rinse cycle contain cationic surfactants.

Examples of the cationic surfactants which can be used in the agents according to the invention are especially quaternary ammonium compounds. Ammonium halides such as Alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methylammonium chloride, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldi methylbenzylammonium chloride and tricetylmethylammonium chloride. More fiction The quaternized protein hydrolyzates represent usable cationic surfactants.

Silicone oils such as those commercially available are also suitable according to the invention available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino mo differentiated silicone, also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer Steller: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines such as that under the name Tego Amear®S 18 available stearylamidopropyldimethylamine, are characterized by a good one conditioning effect especially due to its good biodegradability.

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as those sold under the Stepantex® and Dehyquat® trademarks Methylhydroxyalkyldialkoyloxyalkylammonium methosulfates.  

This is an example of a quaternary sugar derivative that can be used as a cationic surfactant Commercial product Glucquat®100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride ".

The detergents and cleaning agents according to the invention can be either in solid to gel-like as well as powder, granules, extrudates or as shaped bodies (tablets) available. The individual forms are by conventional manufacturing processes, the expert are known from the prior art, can be produced.

In the agent according to the invention, the active ingredient is incorporated in such a way that it or wash cycle (and also in optional pre-rinse cycles) not or only in a subordinate one Dimensions is released. This ensures that the active ingredients only in the final rinse cycle Make an impact. In addition to this chemical packaging, depending on the type Dishwasher or textile washing machine a physical assembly required so that the active ingredient-containing particles do not change when the water is changed in the machine are pumped out and are therefore no longer available for rinse aid.

Domestic dishwashers contain, for example, in front of the drain pump, which the water or the cleaning solution after the individual cleaning cycles the machine pumps, a sieve insert that clogs the pump due to dirt residues should prevent. The packaging of the active ingredient used is regarding its Size and shape preferably designed so that it fits the strainer Dishwasher after cleaning, d. H. after exercise stress the machine and the cleaning solution. This ensures that the active ingredient is present in the rinse cycle and only in this rinse cycle is released and brings the desired rinse aid effect. As part of the present Automatic dishwashing agents preferred according to the invention are characterized in that the the preparation containing the active ingredient or the active ingredient itself is packaged in such a way that they have particle sizes between 0.1 and 35 mm, preferably between 1.0 and 25 mm and in particular between 2 and 20 mm.

In one embodiment of the present invention, the preparations or Particles of customary powdery or granular dishwasher detergents are added.

In a further preferred embodiment, the particles together with the Ingredients of machine dishwashing detergents to form a combination product  Dishwasher detergent and rinse aid processed. Such products are preferred so-called shaped bodies, also referred to in the art as tablets.

The combination products can be produced in a manner known per se. In In one possible embodiment, the moldings and those according to the invention Particles produced separately and then connected to each other, the Shaped bodies already have recesses prepared for the particles. The connecting can, for example, by simply inserting it into the recess or gluing the two fixed components.

In a further embodiment, the particles according to the invention or the Premix for this in a suitable tabletting device with the premix for the Dishwashing detergent processed into moldings.

In the washing and cleaning agents according to the invention, the active ingredient containing preparation with the above-mentioned sizes from the matrix of the others Particulate ingredients protrude, but the other particles can also Have sizes that are in the range mentioned, so that a washing and Detergent is formulated that consists of large detergent particles and the active ingredient containing particles. Especially when the particles containing the active ingredient are colored, for example have a red, blue, green or yellow color it for optical reasons for the appearance of the product, d. H. of the entire Cleaning agents are an advantage if these particles are visibly larger than the matrix the particles of the other ingredients of the agent. Here are inventive Particulate detergents and cleaning agents are preferred, which (without considering the Rinse aid particles) particle sizes between 200 and 3000 microns, preferably between 300 and 2500 µm and in particular between 400 and 2000 µm.

The optical appeal of such compositions can, in addition to the coloring of the Preparation containing active ingredient also by contrasting coloring of the powder matrix or be increased by the form of these preparations. Because in the manufacture of the Preparations containing active ingredient on technically uncomplicated processes can be used, it is easily possible to use them in the most varied of ways Offering shapes. In addition to the particle shape, which can be spherical in shape For example, cylindrical or cube-shaped particles can be produced and used. Others too geometric shapes can be realized. Special product designs can for example, contain the active ingredient as star-shaped preparations. Even discs  or forms that form the base of plants and animal bodies, for example trees, flowers, Show bloom, sheep, fish, etc. can be easily produced. Interesting visual incentives can also be created in this way that if the active ingredient in the Rinse cycle of a machine dishwashing process is released in the form of a manufactures stylized glass to visually underline the rinse aid effect in the product. There are no limits to your imagination.

If the cleaning agents according to the invention are formulated as a powder mixture, especially with very different sizes of active ingredient preparation, the z. B. Rinse aid particles and detergent matrix - on the one hand when the package is shaken partial segregation occurs, on the other hand the dosage can be divided into two successive cleaning cycles may be different since the consumer is not Always the same amount of detergent and active ingredient, e.g. B. rinse aid, dosed. Should be technically always the same amount per cleaning cycle, this can be done via the packaging of the agent according to the invention which is familiar to the person skilled in the art Bags made of water-soluble film can be realized. Also particulate washing and Detergents, where a dosing unit in a bag made of water-soluble film is welded, are the subject of the present invention.

As a result, the consumer only has one bag, for example a Detergent powder and several optically prominent in special preparations contains incorporated active ingredients in the dosing compartment of its washing or Put in the dishwasher. This embodiment of the present invention is therefore a visually appealing alternative to conventional detergent tablets.

Examples example 1

A machine dishwashing detergent was produced in the following way:

60% by weight of the rinse aid surfactant Polytergent SLF 18B45 from Olin is reduced to 15% by weight of the carrier material Polytrap from Advanced Polymer Systems, so that a free-flowing granulate is formed. This is mixed with 25% by weight of PEG 6000 and in a tablet press into 1 g tablets. On these pellets is through repeated immersion in an 8% solution of poly-N-isopropylacrylamide (PIPAAm) in Acetone / isopropanol 40:60 applied a coating of the LCST polymer. To Drying the solvent is again a paraffin coating in the immersion process applied with a melting point of 50 ° C.

This preparation is dosed in various ways together with an ordinary dishwashing detergent (Somat; commercial product of the applicant):

• 1. It is put into the dosing box of the together with commercially available Somat powder cleaner Dishwasher given.
• 2. It is glued into a cavity of a Somat cleaner tablet or inserted loosely.
• 3. It is in a tablet press in the loose premix of a Somat cleaner tablet inserted and pressed together with this to a shaped body.

The function of these detergent assemblies is then described in one commercial household dishwasher from Miele G 683SC tested. It shows in all cases, as desired, that the Somat cleaner is available both as a powder and dissolves as a tablet in the cleaning cycle (either 55 ° C or 65 ° C program) while receive the formulation containing the rinse aid until the start of the rinse aid cycle remains. It disintegrates in the first minutes of the rinse cycle and sets it as desired Rinse aid free.

Example 2

Pellets with a higher rinse aid surfactant content are formulated as follows: 72% by weight of the rinse aid surfactant Polytergent SLF 18B45 from Olin is reduced to 18% by weight of the carrier material Polytrap from Advanced Polymer Systems, so that A free-flowing granulate is formed and mixed with 10% by weight of PEG 6000 and in a tablet press into 1 g tablets. Then continue as in Procedure described in Example 1.  

Example 3

The 3 components (Polytergent, Polytrap and PEG 6000) can also be combined in one Mixers are mixed so that a very homogeneous, easily formable mixture is formed. This can be done either in the extruder or as a melt as described in Example 1 process further.

Example 4

A machine dishwashing detergent is produced in the following way: As in Example 1, 60% by weight of the rinse aid is on 20% by weight of the carrier material applied so that a free-flowing granulate is formed. 20% by weight of these granules are mixed with a 10% solution of PIPAAm in acetone. After extensive Evaporation of the solvent gives the granules obtained in a tablet press Pressed pellets of about 1 g. These compacts are then in the Dip process coated with paraffin (melting point 50 ° C).

The assembly with the cleaner and the function test are analogous to Example 1 executed. Here too one observes that the rinse aid containing up to Start of rinse aid does not decay, but then during the first minutes of Rinse aid disintegrates and releases the rinse aid.

Example 5

The rinse aid-containing preparation is carried out as in Example 1 or in Example 2 using the Difference that there is no paraffin coating. The rinse aid containing LCST Polymer-coated compact is put into the loose premix in a tablet press Somat cleaner tablet inserted and together with this to a shaped body pressed so that it is roughly at its center. Through this packaging ensures that the LCST polymer does not come into contact with cold rinse water, as long as the surrounding cleaner is not yet dissolved. After its dissolution, the The rinse liquor is already so hot that the LCST and rinse aid levels are exceeded The formulation does not disintegrate until the rinse aid starts, but in the first Minutes disintegrates and releases the rinse aid as desired.

Claims (16)

1. washing and cleaning agents containing usual ingredients, characterized in that it contains an active ingredient preparation which is made up with an LCST polymer. 2. Detergent and cleaning agent according to claim 1, characterized in that the Active ingredient made up with the LCST polymer after heat treatment in a liquid medium in the main rinse or wash at least partially remains unchanged and after a temperature decrease following the Heat treatment is released. 3. washing and cleaning agent according to claim 1 or 2, characterized in that the active ingredient is coated or coated with an LCST polymer. 4. washing and cleaning agent according to claim 1 or 2, characterized in that the drug preparation is embedded in a matrix of an LCST substance is. 5. washing and cleaning agent according to claim 1 to 4, characterized; that the LCST polymer is selected from cellulose derivatives, mono- or di-N- alkylated acrylamides, copolymers of mono- or di-N-substituted Acrylamides with acrylamides and / or acrylates or acrylic acids. 6. washing and cleaning agent according to claim 5, characterized in that the LCST polymer is selected from cellulose ethers, polyisopropylacrylamide, Copolymers of polyisopropylacrylamide and blends of these substances. 7. washing and cleaning agent according to one of claims 1 to 6, wherein the lower critical separation temperature of the LCST substance is between 20 ° C and 90 ° C. 8. Detergent and cleaning agent according to one of claims 1 to 7, thereby characterized in that the heat treatment at a temperature between 20 ° C and 150 ° C, preferably between 30 ° C and 90 ° C is carried out. 9. washing and cleaning agent according to one of claims 1 to 8, characterized characterized in that the made-up active ingredient preparation with another  Substance is coated, which is at a temperature above the lower Demixing temperature of the LCST substance is soluble or a melting point above this temperature or has a delayed solubility. 10. washing and cleaning agent according to one of claims 1 to 9, characterized characterized in that the agents in solid to gel form, as a powder, Granules, extrudates or as moldings are present. 11. Washing and cleaning agent according to one of claims 1 to 10, characterized characterized that it is a textile detergent and as active ingredients Finish components, enzymes, fragrances, dyes, fluorescent agents, optical Brighteners, anti-shrink agents, anti-crease agents, antimicrobial agents, Germicides, fungicides, antioxidants, antistatic agents, ironing aids, repellents and Contains impregnating agents, UV absorbers and any mixtures of the above. 12. Detergent and cleaning agent according to one of claims 1 to 10, characterized characterized that it is an automatic dishwashing detergent and as an active ingredient Rinse aid, fragrances, dyes, bleach, preferably an active chlorine carrier, contains. 13. Washing and cleaning agent according to claim 12, characterized in that the Active ingredient preparation is a particulate rinse aid. 14. Washing and cleaning agent according to claim 12, characterized in that the particulate rinse aid particle sizes between 0.1 and 35 mm, preferably between 1.0 and 20 mm and in particular between 2 and 20 mm. 15. washing and cleaning agent according to one of claims 12 to 14, characterized characterized in that the active ingredient preparation is powdery or granular Dishwasher detergent is added. 16. Washing and cleaning agent according to one of claims 12 to 14, characterized characterized in that the active substance preparation is embedded in a shaped body.